Nontarnishing detergent compositions



United States Patent N ONTARNISHING DETERGENT COL [POSITIONS Charles H. Schramm, Hillsdale, N; .L, assignorto Leven Brothers Company, New York, N; Y., a corporation of Maine No Drawing. Application July 12,-1954 Serial No. 442,895

23 Claims. c1. z's2 137 This invention relates to cleaning compositions containing tarnish inhibitors and more particularly to polycially if the solutions are at elevated temperatures and;

are allowed to remain in contact with the metal for several minutes. Since German silver is frequently used for household articles commonly washed in polyphospirate-built detergent compositions, it is evident that this is a serious problem. a

in accordance with the instant invention polyphosphate and detergent compositions are provided containing a tarnish inhibitor which compositions will not tarnish copper, and nickel and copper alloys such as German silver. stituted guanamine (2,4-diamino-s-triazine) which is.described by the following formula:

where at least one R is a hydrocarbon or hetero'cyclic radical and can be selected from the group consistingof aliphatic, aryl, mixed alkylene aryl, mixed phenylene heterocyclic and mixed alkyl'eneheterocyclic hydrocarbon radicals, and the other R radicals can be hydrogen or any of the radicals selectedfrom the above-mentioned:

group.

WhenR is an aliphatic hydrocarbon group" it can have-either a straight or branched chain, and can be saturated or unsaturated.

The number of carbon atoms in the R" groups is'ir'n-- portant. Form'oguanamine' is not effective. Good tarnish-inhibiting properties appear when at' least one" of R R R3, R1; or R is a' radical having three carbon atoms and theremaining R groups are hydrogen, but relatively large amounts of such guanamines may be necessary for complete protection. Tarnish-inhibiting ability materially improves as the' R groups increase further in molecular weight; and lesser amounts of guanamine can be used; Optimum tarnish-inhibiting properties are displayed by compounds; in which the sumof the R groups-is from seven to seventeen carbon atoms, especially compounds in which at least one'R has from seven to seventeencarbon atoms, and. invsuch compounds the number of carboniatoms in the remaining R groups is .not critical, .although the lower alkyl groups,

Aqueous solutions of polyphosphates The tarnish inhibitor of the invention is a sub-- '2 i. e., those having from one to about five carbon atoms, and hydrogen are preferred.-

Typical R radicals are straight and branched chain methyl, ethyl, propyl, heptyl, octyl, nonyl, butyl, hexyl, decyl, undecyl, dodecyl, tri'decyl, tetradecyl, pentade'cyl, decenyl, heptylenyl, hexadecyl, heptadecyl, decynyl, dodecenyl, octa'de'cenyl, oct'adecadienyl, dodecynyl, the mixed alkyl radicals derived from fatty' oils such as palm oil, rapeseed oil, tall oil, linseed oil, etc., phenyl, benzyl, phenyl guanamyl, decylene guanamyl and octylene guanamyl. These can be taken in any combinations meeting the above requirements.

The following are some typical guanamines in accordance with the invention:

(5) a N H:

The mixture of the nitrile, acid or ester and biguanide is heated at an elevated temperature, say 180 C., for several hours. Temperatures from 120 to 250 C. have been found satisfactory.

The crude mixture which is obtained as a result of this reaction can be used without further purification and consists mainly of the substituted guanamide and, in the case of acid or ester reactants, of the amide of the acid or ester starting material in approximately equal amounts. The guanamine has been isolated and shown to be the principal antitarnishing constituent of the mixture.

The guanamines in accordance with the invention are nontoxic, sparingly water-soluble substances, but sufficiently water-soluble to permit their incorporation in polyphosphate and synthetic detergent solutions in the amounts required to impart tarnish inhibition thereto.

An amount of the guanamine would be added to the polyphosphate and/or synthetic detergent composition suflicient to give tarnish inhibition when the composition is used in its normal way. Usually about 0.1% of the guanamine gives adequate tarnish inhibition, but larger amounts can be used if desired. From 0.1 to 5% is efiective under nearly all conditions and therefore is preferred. The maximum amount of guanamine is not critical but more than is necessary to give the desired effect usually would not be used, and of course an amount in excess of that soluble in the solution would not be used. It will be understood that the amount required will depend in part upon the tarnish-inhibiting properties of the particular guanamine in question, upon the tendency of the polyphosphate and/or synthetic detergent with which it is used to tarnish copper and nickel alloys and copper alloys, and upon the amounts of polyphosphate and synthetic detergent present.

The guanamines of the invention are effective as tarnish inhibitors in both hard and soft water.

The tarnish inhibitors of the invention are effective with water-soluble polyphosphates as a class at pH values where such polyphosphates tend to tarnish German silver (usually pH 6 or above) and particularly those polyphosphates identified by the following general formula from which it is seen that both the acids and their various salts are contemplated:

[(M M M PO minus b(MOM)] where:

M M and M are hydrogen or an alkali metal, such as sodium, potassium and ammonium, and can be the same or different, and M is M and/ or M and/or M a is an integer of l or more, usually 1 to 4,

I b is an integer of 1 or more, usually 1 or 2,

x'is an integer of 1 or more, usually 1 to 6.

. invention.

Among the polyphosphoric acids and their alkali metal salts coming within the invention are the polymetaphosphoric acids (HPO (a is 1, b is 1, x is more than 1), pyrophosphoric acid H P O (a is 2, b is 1, x is 1), triphosphoric acid H P O (a is 3, b is 2, x is 1), and tetraphosphoric acid H P O (a is 4, b is 3, x is 1). Na P O K4P2O7, Na4P207, Na H P2O7, Na5P4013, Sodium Polyphos (Na P O --Blockson), K (PO -2H O, Pascals salt, sodium dimetaphosphate, sodium trimetaphosphate (Knorres salt), sodium tetrametaphosphate and sodium hexametaphosphate (Grahams salt) are examples.

The guanamine tarnish inhibitors can be incorporated in compositions containing polyphosphates, and in compositions containing synthetic detergents, and are efiective to reduce tarnish due to polyphosphate or detergent in each of these types of compositions. They are particularly useful in synthetic detergent compositions which contain one or more polyphosphates as builders and one or more synthetic detergents, i. e., anionic detergents, cationic detergents, nonionic detergents, and mixtures thereof. In many instances they display an enhanced fifteen carbon atoms. whose preparation and properties are set forth in U. S.

tarnish-inhibiting:action in the presence of both-polyphosphate and detergent.

The polyphosphate-built detergent compositions. should contain conventional proportions of active detergent, usually within the range between '5 to 40%, polyphosphate in any amount, usually between 5 to-50%, based on the total composition, and the residue builders and inert materials.

The guanamines are useful with a wide variety of anionic, cationic and nonionic synthetic detergents, with and without polyphosphates.

The alkyl aryl sulfonates are a class of detergents well known in the art under this name. One example thereof are the sulfonated phenylpolypropylene alkanes, charac- -terized by thebranched chain structure of polypropylene and a tertiary alkyl carbon at the benzene ring, and having the following general structure:

CHzRz where M is hydrogen, an alkali metal or an organic amine cation, and R and R are alkyls, of the type formula C H and at least one R is a polypropylene group, the whole alkyl group containing preferably twelve to These are known compounds,

Patent No. 2,477,383 to Lewis, issued July 26, 1949; they are available in'commerce' under the trade names Oronite, Ultrawet and Neolene.

Another class of useful detergents are the amidoalkane sulfonates which are characterized: bythe following structure:

where A is hydrogen oran alkali metal, i. e., ammonium, I

sodium, or potassium, n is a small whole number from one to about five, preferably two or three, R is hydrogen, or an alkyl, aryl, or cycloaliphatic group, such as methyl, and R is an alkyl'or alkylene radical, such as myristyl, palmityl, oleyl and stearyl. Sodium palmitic tauride, so-

"dium palmitic methyl tauride, sodium myri'stic methyl tauride, sodium palmitic-jstearic methyl-tauride and sodium pahnitic methyl amidopropane-sulfonatehave been found to be particularly suitable for use in the compositions of the invention.

These compounds are prepared by interacting the corresponding aliphatic acid anhydride or halide with an or- V ganic aliphatic aminosulfonic acid, such as taur'ine and the various N substituted taurines, such as N-methyl taurine, or aminopropane sulfonic acid;-NI-I (CH SOH.

The invention is also applicable to 'other-water-soluble alkyl aromatic sulfonic acids, such as those prepared by alkylating benzene or naphthalene with a kerosene frac- G and. thioether-andester.detergentshaving the following general formula:

R-A-tcrn Hte-it-.cH-l- Hz n where R is a straight or branched chain saturated or unsaturated hydrocarbon group having from eight to eighteen carbon atoms or an, aralkyl group having a straight or branched saturatedor unsaturated hydrocarbon group of' from eight to eighteen carbon atoms attached to the aryl nucleus, and attached to A through the aryl nucleus, A is selectedfrom the group consisting ofethereal oxygen and-sulfur,jca'rboxylic esterand thiocarboxylicester groups and x is a. number'from eight to twenty. R can for examplebe a straight or branched chain octyl, nonyl, decyl, lauryl, myristyl, cetyl or stearyl group, or an alkyl aryl group such as octylbenzene, nonylbenzene, decylbenzene, stearylbenzene, etc.

Thevsulfated ethoxynatdfderivatives of the. above. also are useful. anionic detergents:

whereMis hydrogen or an alkalimetal or organic amine cation and x, A and R areas: above.

When R is alkyl it will be evident that the detergent can be regarded as derived from an alcohol, mercaptan, oxy or thio fatty acid ofhighmolecular weight, by condensa'tion with ethylene oxide. Typical of this type of alkyl ether are the condensation-products of oleyl or 'dodecyl alcohol orrn'ercaptan .with from eight to seventeen 'zmoles of ethylene oxide, such -'as Emulfor ON, Nonic 218 and .SteroxI SE andSK. Typical alkyl 'esters are 61226 and R'enex (polyoxyethyleneester of tall oil acids), Sterox CD and Neutronyx 330 and 331 (higher fatty acid esters of polyethylene glycol).

R is aralkyl, the detergent can be derived from an alkyl phenol or thiophenol.

The ethoxynated alkyl phenols and thiophenols have the following general formula:

where R is a straight or branched saturated or unsaturated hydrocarbon group having at least eight carbon atoms up to. approximately eighteen carbon atoms, A is oxygen or sulfur and x is a number from eight to twenty. R can, for example, be a straight or branched chain octyl, nonyl, decyl, lauryl, cetyl, myristyl or stearyl group. Typical are the condensation products of octyl and nonyl phenol and thiophenol with from eight to seventeen moles of ethylene oxide, available commercially under the trade names NIW, Antarox A-400, Igepal CA and CO, Triton X-100, Neutronyx 600 and Tergitol NFX.

The detergent composition can contain supplemental builders including alkali metal and alkaline earth metal sulfates, chlorides, silicates, borates, carbonates, metaphosphates, and orthophosphates, such as sodium silicate, magnesium sulfate, sodium tetraborate, sodium carbonate, sodium sulfate, trisodium phosphate, potassium carbonate, disodium orthophosphate, sodium metaphosphate, calcium sulfate, calcium chloride, sodium chloride, sodium borate and potassium metaphosphate. The builder should but need not be water-soluble.

In addition to or instead of the above-mentioned supplemental inorganic salts, organic materials such as starch, polyethylene glycols, polyvinyl alcohols and salts of carboxymethylcellulose can be used as builders. It has been found that between about 0.1 and 1% of an al- -kali--metal carboxymethylcellulose increases detergency "and" sudsing.

The builder mixture is so chosen among alkaline, neutral and acidic salts that the composition obtained in an aqueous 0.14% washing solution has a pH of 7 or above. Preferably, its pH lies within the range from 7 8 for one-ha1f hour. The efiectiveness of the inhibitor is rated as follows:

Excellent=no more than slight or barely noticeable cast,

uniform or spotted.

to about 10 since solutions which are more alkalinebrnay Fair=very Slight to considerable attack be to the 5km and tend to weaken P fa Tarn=severely tarnished, same as when inhibitor is ab particularly woolens. In general, the alkali metal car- Sent. bonates are preferred agents for bringing the pH of the solution to a high alkaline value within the preferred EXAMPLES 1 To 4 I Detergent compositions were prepared having the fol- The detergent composition is prepared by conventional lowing f latio methods, as by blending the ingredients thereof in an percent aq u solution or slurry and then drymg the result- Sodium Oronite (active) (sodium phenylpolypromg mixture in a spray or drum dryer at elevated tempylene lf t p Tetrasodiurn pyrophosphate 30.0 The tarnish inhibitor may be added to the polyphoss i tripolyphosphate 15 phate or detergent composition at any stage of its manu- Sodium carboxymethylcellulose 0.5 facture, to the finished polyphosphate or detergent coms di i1i 6,0 position, or to the polyphosphate or detergen solution. Sodium carbonate 3.0 The guanamines employed in the following examples s di ulfat and i 20,5 were prepared by heating mixtures of biguanide and the Water 7.0 corresponding nitrile at ISO-200 C. for about two to four hours. 1:1 molar ratios were taken of biguanide 10() and the nitrile. The crude product was used unless other- Wi in i Guanamine 1 0.02 to 5 2 33 212; g f i g f s P actlon of the composl' 1 0.044 to 11.1% based on the weight of the polyphosphates. Five grams (dry Solids basis) of the composition to To solutions of these compositions were added the alkyl be tested is dissolved in one quart of distilled water and 30 guanammes hsted f table below m the amount 300 ml. of the test solution placed in a suitable container F for compalilson purposfis was Prepared and brought to 1 0 F, A Strip f German silver metal which did not contain any tarnish inhibitor. The solui polished with a t l polish, h d d d i d, placed tions then were tested for tarnish inhibition in accordance in the olutio d th ol ti h ld t t F, with the above-described test with the following results:

Table I Percent Inhibitor Example No. Inhibitor Control N n Tarn. Tarn. Tarn. Tarn NIL-C (E-NH: Tarn. Tarn. Tarn. Tarn.

Formoguanamine NHr- (E-NH-Q Tarn. Exc. Exc. E10.

4-N-Pheny1 Formoguanamine C gHu 3 t Z NHz- NH: Tarn. Exc. 1510. Fair.

Stearoguannmine NHy-i') JJ-NH; Tarn. Exc. Exc. Exo.

Lauroguanamtne Exc.=exceilent.

Itzis evident. from'the above results thatzformoguanamine,

a guanamin'ewithout an-R' substituent,.is.-noteifective as a tarnishinhibitor. -A compound in which oneo'f R R R R -or R is an alkyl radical oranaryl radical and the remainin Rsh drogen is effective, however,lasfevidenced by 4aN-pheny1 formoguanamine, a compound where R, is phenyl, and'stearoguanamineand lauroguanamine, com- .pounds Where R is a higher alkyl group.

Thecompositions also were "evaluated for-their sud sing properties. This Wasdoneusing the Terg-O-Tometer em-- ploy-ing thefollowingprocedurezl2.64 g. of thedetergent composition Without the tarnish inhibitor was weighed into:a 100 ml. beakerand 'the appropriateamount'of the tarnish inhibitor tobe testedwas added. "'Fifty mL of SO p.;p.-m. Waterwas'then added and the solids brought 'into solution with the aid of heat; The solution was-diluted to 1,000 ml. with 50 p. p..-m. water, brought to 120 F. and placed in the cup of a standard Terg-O-Tometer. 0.75 g. vacuum cleaner dust soil was then added, followed by twelve 4 /2" x 6" pieces of desized cotton sheeting. The paddles of the. Terg-O-Tometer were operated for ten minutes at the rate of eighty-six complete oscillations per minute, while maintaining the temperature of the solutionsat 120 F. After. theten minute:period-thequaritity of suds was visually estimated and' graded according-to the following scheme: I Grade 0=no suds Grade l=trace of suds Grade 2=traceto Ms coverage of surface Grade 4= Ai to coverage of surface 'Grade'-5=% to' /2- coverage of surface Grade 6=% to% coverage ofsurface Grade 7'=% to fullcoverage-of-surface The following results were obtained:

N min-( i (J-NEG 1 1 1 4-N-Phenyl Formoguenamlne "Hrs Stearoguanamlne C uHzs ('1 N N NHr-( 'B I-NR1 1 5 6 Lauroguanamlue 10 The above results: show .thatlauroguanaminefhas excellent suds-boostingtprope'rties. These 'suds-boosting prop- 'erties are not displayed by the other compounds tested,

- showing that compounds having an R group of approximately twelve carbon atoms are unique in this. respect. Similar. suds boo'stin'gproperties. would be expected from compounds having R alk-yl radicals offrom ten tofo'urteen carbon atoms.

Compositions containingv tarnish inhibitors of the-invention do not tarnish copper, nickel-copper-Zi'n-c alloys such as German silver, coinage nickel or brass, whichnorma'lly tarnish whenexposed to aqueous' solutions containing-polyphosphates and/ or synthetic detergents. It isnot possible atthis tim'e to explain whythe-compounds-of theinventhe weight of the-tarnish producin'g substance, i: e.',polyphosphate and/or detergent, unless otherwisestated. In

'theexamples'lfor'ease' of preparation, the weightsofguanamine are given as based'on the dry weightof the total composition.

Thenom'enclature employed'in this application and in the claims for the guanamines conforms with that used in the published literature. See U. S. Patent No. 2,459,710, for example. The guanamines are named in accordance with the acid from which they are prepared. The following table will clarify the relation between the R radicals in the general formulae-in column 1, lines 39-45 and in the claims with-'the'names of'the'guanamines as named elsewhere in the specification and claims:

From Acid RRadl'cal Guan'amine hXd r iq an ml erQp ut r su namm heptyl--. capryloguanaminer hendecyl laurogpanarnlner heptadec s'tearoguanamlne. phenyl. benzoguanamme. phenyleneterephthaloguanamine. guanamyl oxaloguanarnlne. ethylene sueeinoguanamlne. sebacic octylene sebaeoguanamine.

I claim:

1. A detergent composition consisting essentially of a water-soluble substance selected from the group consisting of polyphosphates and synthetic organic nonsoap anionic and nonionic detergents which in aqueous solution tarnishes copper and copper and nickel alloys and a tarnish inhibitor in an amount to lessen the tarnishing action of the substance and having the general formula:

N /NR4R5 where at least one R is an organic radical selected from the group consisting of hydrocarbon and guanamine radicals having at least three carbon atoms, and the remain ing R radicals are selected from the group consisting of hydrogen, hydrocarbon, and guanamine radicals.

2. A detergent composition in accordance with claim 1 in which at least one R radical has from seven to seventeen carbon atoms.

3. A detergent composition in accordance with claim 1 which the tarnish inhibitor is lauroguanamine.

4. A detergent composition in accordance with claim 1 in which the tarnish inhibitor is capryloguanamine,

5. A detergent composition in accordance with claim 1 in which the tarnish inhibitor is stearoguanamine.

6. A detergent composition in accordance with claim 1 in which R; is the mixed alkyl radicals derived from a naturally-occurring fatty oil.

7. A detergent composition in accordance with claim 1 in which R is a mixed alkylene aryl radical.

8. A detergent composition in accordance with claim 1 in which R is a mixed alkylene guanamine radical.

9. A detergent composition in accordance with claim 1 in which R is a mixed phenylene guanamine radical.

10. A detergent composition in accordance with claim 1 in which R is phenyl.

11. A detergent composition in accordance with claim 1 in which R is phenyl.

12. A detergent composition in accordance with claim 6 in which the fatty oil is palm oil.

13. A detergent composition in accordance with claim 6 in which the fatty oil is rapeseed oil.

14. A detergent composition in accordance with claim 6 in which R is the mixed alkyl radicals derived from tall oil.

15. A detergent composition in accordance with claim 7 in which the mixed alkylene aryl radical is benzyl.

16. A detergent composition consisting essentially of a water-soluble polyphosphate which in aqueous solution tarnishes copper and copper and nickel alloys and a tarnish inhibitor in an amount to lessen the tarnishing action of the polyphosphate and having the general formula:

where at least one R is an organic radical selected from the group consisting of hydrocarbon and guanamine radicals having at least three carbon atoms, and the remaining R radicals are selected from the group consisting of hydrogen, hydrocarbon, and guanamine radicals.

17. A detergent composition in accordance with claim 16 in which the amount of tarnish inhibitor is within the range from 0.5 to 5% by Weight of the polyphosphate.

18. A detergent composition in accordance with claim 16 in which the polyphosphate is a tripolyphosphate.

19. A detergent composition in accordance with claim 16 in which the polyphosphate is a pyrophosphate.

20. A detergent composition in accordance with claim 16 in which the polyphosphate is a polymetaphosphate.

21. A detergent composition consisting essentially of a water-soluble synthetic organic nonsoap detergent selected from the group consisting of anionic and nonionic detergents which in aqueous solution tarnishes copper and copper and nickel alloys and a tarnish inhibitor in an amount to lessen the tarnishing action of the detergent and having the general formula:

where at least one R is an organic radical selected from the group consisting of hydrocarbon and guanamine radicals having at least three carbon atoms, and the remaining R radicals are selected from the group consisting of hydrogen, hydrocarbon and guanamine radicals.

22. A detergent composition in accordance with claim 21 in which the detergent is a phenylpolypropylene sulfonate.

23. A detergent composition in accordance with claim 21 in which the detergent is a condensation product of an alkylene oxide and an organic compound reactive therewith, selected from the group consisting of higher fatty carboxylic and thio carboxylic acids and higher fatty alcohols and mercaptans.

Schaeflt'er Nov. 18, 1952 Schaefier Nov. 18, 1952 UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,848,420 August 19,1958 Charles H. Schramm It is hereby certified that error appears in the printed specification of the above numbered gatent requiring correction and that the said Letters Patent should read M as correcte below.

Column 8, Table I, second column thereof, opposite Example No. 3, the formula should appear as shown below instead of as in the patent. HHSE column 10, line 72, after the claim reference numeral 1 insertin-.

Signed and sealed this 28th day of October 1958.

Attest: KARL H. AXLINE, ROBERT C. WATSON,

Attestz'ng 0772mm omm'ssz'oner of Patents. 

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A WATER-SOLUBLE SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF POLYPHOSPHATES AND SYNTHETIC ORGANIC NONSOAP ANIONIC AND NONIONIC DETERGENTS WHICH IN AQUEOUS SOLUTION TARNISHES COPPER AND COPPER AND NICKEL ALLOYS AND A TARNISH INHIBITOR IN AN AMOUNT TO LESSEN THE TARNISHING ACTION OF THE SUBSTANCE AND HAVING THE GENERAL FORMULA: 